Physical and mechanical characterization of nanocomposites with carbon nanotubes functionalized with the matrix polymer

Single wall carbon nanotubes (SWNT) are functionalized with poly(vinyl alcohol) (PVA). The functionalized nanotubes are homogeneously dispersed in a PVA solution. Nanocomposite films with low SWNT content (0.1 to 1%) are produced by the wet-casting method. X-ray diffraction shows that the PVA crystallinity was not affected by the presence of the SWNT. The improvement in tensile modulus and strength at such low reinforcement loadings is indicative of good interfacial bonding between the functionalized nanotubes and the polymer matrix.     

A comparison of the mechanical strength and stiffness of MWNT-PMMA and MWNT-epoxy nanocomposites

The surface of multi-wall carbon nanotubes (MWNTs) was functionalized by covalent linking of long alkyl chains. Such functionalization led to a much better tube dispersion in organic solvents than pristine nanotubes, favored the formation of homogenous nanocomposite films, and yielded good interfacial bonding between the nanotubes and two polymer matrices: a thermo-set (Epon 828/T-403) and a thermoplastic (PMMA). Tensile tests indicated, however, that the reinforcement was greatly affected by the type of polymer matrix used. Relative to pure PMMA, a 32% improvement in tensile modulus and a 28% increase in tensile strength were observed in PMMA-based nanocomposites using 1.0 wt% nanotube filler. Contrasting with this, no improvement in mechanical properties was observed in epoxy-based nanocomposites. The poorer mechanical performance of the latter system can be explained by a decrease of the crosslinking density of the epoxy matrix in the nanocomposites, relative to pure epoxy. Indeed we demonstrate that the presence of nanotubes promotes an increase in the activation energy of the curing reaction in epoxy, and a decrease of the degree of curing.     

Micromechanical properties of poly(butylene terephthalate) nanocomposites with single- and multi-walled carbon nanotubes

Polymer nanocomposites with carbon nanotubes (CNT) are becoming important structural materials because of their superior mechanical properties and easy processability. The objective of the work is to investigate the influence of small amounts of single walled carbon nanotubes (SWCNT), as well as multi-walled carbon nanotubes (MWCNT), on the microhardness of a thermoplastic polymer such as poly(butylene terephthalate) (PBT). The nanocomposites were obtained by introducing the CNT into the reaction mixture during the synthesis of PBT. The polymers without carbon nanotubes (reference material) and with carbon nanotubes were synthesized using an in-situ polycondensation reaction process. Weight percentages ranging from 0.01 to 0.2 wt% of the single walled and from 0.01 to 0.35 wt% of the multi-walled nanotubes were dispersed in 1,4-butanediol (BD) by ultrasonication and by ultra high speed stirring. The nanocomposites were extruded followed by injection molding. The samples were characterized by electron microscopy and microindentation hardness techniques. The variations of the micromechanical properties (indentation hardness) of the nanocomposites with nanotube content and with temperature are discussed in the light of the stress transfer between the polymer matrix and nanotubes, the degree of dispersion, the nature of the tubes and other structural parameters.     

ESR Investigations on Polyethylene–Fluorine Functionalized Single Wall Carbon Nanotubes Composites

Electron spin resonance investigations on nanocomposites obtained by dispersing fluorinated single walled carbon nanotubes within polyethylene are reported. Three resonance lines assigned to uncoupled electronic spins confined within magnetic impurities, amorphous carbon, and single wall carbon nanotubes have been observed. The temperature dependence of these lines is analyzed in detail and used to assign each component of the as-recorded ESR spectrum to a precise component of the nanocomposite. Magnetic impurities are originating from catalysts residues (in our case, Fe impurities). Surprisingly, the narrowest line is due to paramagnetic defects (amorphous carbon) while the broad line originates from electrons delocalized over conducting nanotubes. The broadening of this line reflects a bottleneck in the relaxation mechanism, triggered by the interaction of the uncoupled electrons localized on carbon nanotubes with the magnetic impurities.     

Nanocomposites based on multiblock polyester elastomers (PEE) and carbon nanotubes (CNT)

Polymer nanocomposites including those containing carbon nanotubes appear to be of particular significance. Polymer nanocomposites based on thermoplastic poly(ether-ester) elastomer and carbon nanotubes have been prepared and investigated. The nanocomposites are obtained (in situ) by introducing the fillers into the reaction mixture and the synthesis of copolymer by polycondensation in the molten state. The nanotubes are dispersed in 1,4-butanediol by ultrasonication. Physical properties of the resulting nanocomposites are studied using the DSC, DMTA, SEM and mechanical tensile tests.     

Melt mixing of polycarbonate/multi-wall carbon nanotube composites

—Composites of polycarbonate (PC) with multi-wall carbon nanotubes (MWNT) of different concentrations are prepared by diluting a PC based masterbatch containing 15 wt% MWNT using melt mixing in a DACA-Micro Compounder (4 g scale). Electrical resistivity measurements indicate that the percolation of MWNT is reached between 1 and 1.5 wt%. In addition, melt rheology was applied as another sensitive method to detect the percolation of the nanotubes. Atomic Force Microscopy and visual observations of the composite dispersions in a PC-solvent were used to characterise the state of MWNT dispersion. Differential Scanning Calorimetry and Dynamic Mechanical Analysis were applied to detect changes in the glass transition temperature of PC as a result of processing and of MWNT interactions with the PC matrix including the state of dispersion. In addition, DMA confirmed the reinforcement effect of the nanotubes. The results show that the nanotube incorporation also influences the processing behaviour. Due to the enhancement in melt viscosity by adding nanotubes and the enhanced shear forces, the molecular weight of the PC in the composites is reduced as compared to PC extruded under the same conditions. This effect leads to changes in the glass transition temperature and modulus which counteracts the effects originating from the nanotube-polymer interaction.     

170keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响

碳纳米管具有优异的导电性, 是未来电子元器件的理想候选材料, 应用前景广阔. 针对碳纳米管在空间电子元器件的应用需求, 本文研究了170 keV质子辐照对多壁碳纳米管薄膜微观结构与导电性能的影响. 采用扫描电子显微镜(SEM)、拉曼光谱仪(Raman)、X射线光电子能谱仪(XPS)及电子顺磁共振谱仪(EPR)对辐照前后碳纳米管试样的表面形貌和微观结构进行分析; 利用四探针测试仪对碳纳米管薄膜进行导电性能分析. SEM分析表明, 170 keV质子辐照条件下, 当辐照注量高于5×10¹⁵ p/cm² (protons/cm²)时, 碳纳米管薄膜表面变得粗糙疏松, 纳米管发生明显弯曲、收缩及相互缠结现象. 目前, 质子辐照纳米管发生的收缩现象被首次发现. 基于Raman和XPS分析表明, 170 keV质子辐照后碳纳米管的有序结构得到改善, 且随辐照注量增加, 碳纳米管的有序结构改善明显. 结构的改善主要是由于170 keV质子辐照碳纳米管所产生的位移效应导致缺陷重组. EPR分析表明, 随着辐照注量的增加, 碳纳米管薄膜内的非局域化电子减少. 利用四探针测试分析表明, 碳纳米管薄膜的导电性能变差, 这是由于170 keV质子辐照导致碳纳米管薄膜中的电子特性及形态发生改变. 本文研究结果有助于利用质子辐照对碳纳米管膜结构和性能进行调整, 从而制备出抗辐射的纳米电子器件.     

Polypropene nanocomposites by metallocene/MAO catalysts

In our experiments, monospheres (balls of silica, diameter 200–250 nm), carbon fibers (diameter 200 nm, length 0.5–3 mm) and carbon nanotubes (diameter 15–25 nm, length 50 μm) were used as fillers. Before polymerization, the fillers were separated by ultrasound and then treated by methylaluminoxane (MAO). The MAO reacts partially with the OH-groups of the silica and the formation of methane. Catalytically active centers are formed after adding the zirconocenes or other transition metal complexes. The thickness of the polyolefins can be controlled by the pressure of ethene or propene and by the polymerization time. By this method, highly filled nanocomposite polypropenes can be obtained with a silica content of up to 60 wt%. Such combined materials are stiff and hard. Every particle is surrounded by a thin film of polyolefin with a thickness of 30 to 100 nm. Carbon fibers and carbon nanotubes can be covered also within isotactic or syndiotactic polypropene. Because of the hydrophobic character of the carbon surface, the polymer is drawing on the fiber. This leads to a reinforced combined polymer with special properties.     

Electrical conductivity of double-walled carbon nanotubes in the framework of the Hubbard model

The electrical conductivity of double-walled carbon nanotubes of the “armchair” type with the ABAB packing of layers is investigated theoretically. The temperature dependences of the longitudinal electrical conductivity σ(T) for a number of double-walled carbon nanotubes, such as the (3, 3)@(8, 8), (5, 5)@(10, 10), (8, 8)@(13, 13), (10, 10)@(15, 15), and (15, 15)@(20, 20) nanotubes, are obtained in the framework of the Hubbard model with the use of the Green’s function method. It is revealed that the dependences of the electrical conductivity for single-walled and double-walled carbon nanotubes exhibit different behavior in the temperature range from 30 to 60 K. In particular, the dependence of the electrical conductivity for the double-walled carbon nanotubes flattens out in this temperature range.     

Gas-phase synthesis of nitrogen-containing carbon nanotubes and their electronic properties

Nitrogen-containing carbon nanotubes are synthesized using a gas-phase reaction. The synthesis of nitrogen-doped carbon nanotubes from 100 to 500 Å in diameter is accomplished through pyrolysis of acetonitrile (CH₃CN) at a temperature of 800°C. Cobalt and nickel metallic particles formed upon thermal decomposition of a mixture of maleate salts are used as catalysts. The materials synthesized are investigated by scanning and transmission electron microscopy. Analysis of the x-ray photoelectron spectra demonstrates that the content of nitrogen atoms in three nonequivalent charge states is approximately equal to 3%. A comparison of the CK _α x-ray fluorescence spectrum of the carbon nanotubes synthesized through electric-arc evaporation of graphite and the x-ray fluorescence spectrum of the nitrogen-containing carbon nanotubes prepared by catalytic decomposition of acetonitrile indicates that, in the latter case, the spectrum contains a certain contribution from the sp ³ states of carbon atoms. The temperature dependences of the electrical conductivity for different types of multi-walled carbon nanotubes are compared. The difference observed in the temperature dependences of the electrical conductivity is associated with the presence of additional scattering centers in nitrogen-containing carbon nanotubes.     

Kondo效应对磁杂质碳纳米管电输运特性的影响

从碳纳米管中Kondo效应的影响出发, 在有限温度下采用Anderson模型表征碳纳米管/磁杂质系统, 利用Landauer公式对磁杂质碳纳米管的电导和热电势进行研究, 得出和实验结果一致结论. 关键词： Kondo效应 碳纳米管 电输运特性     

碳纳米管材料及应用

碳纳米管自发现以来，由于其独特的结构和奇特的物理，化学和力学特性以及其潜在的应用前景而倍受人们的关注。本文介绍近年来这一前沿研究领域所取得的部分重要研究进展，并讨论碳纳米管的几种应用前景。     

离子轰击控制准直碳纳米管生长的研究

用CH₄,H₂和NH₃作为反应气体，利用等离子体增强热丝化学汽相沉积制备出准直碳纳米管，并用扫描电子显微镜研究了不同负偏压对准直碳纳米管生长的影响. 结果表明，随着负偏压的增大，准直碳纳米管的平均直径减小、平均长度增大. 由于辉光放电的产生，在衬底表面附近形成阴极鞘层，并在阴极鞘层内形成大量的离子和在衬底表面附近形成很强的电场. 离子在电场的作用下对衬底表面的强烈轰击将对准直碳纳米管的生长产生影响. 结合有关理论，分析和讨论了离子的轰击对准 关键词： 准直碳纳米管 离子轰击 负偏压     

Carbon nanotube-epoxy composites: The role of acid treatment in thermal and electrical conductivity

Wet acid oxidation treatment methods have been widely reported as an effective method to purify and oxidize the surface of industrial multi-walled carbon nanotubes. This work examines the use of a concentrated HNO₃/H₂SO₄ mixture in an attempt to optimize the purification procedure of industrial multi-walled carbon nanotubes with diameter distribution statistics. It is shown that acid treatments of several hours are enough to purify the nanotubes. The electrical and thermal conductivities of epoxy composites containing 0.05–0.25 wt% of an acid-treated multi-walled carbon nanotube have been studied. The electrical conductivity of the composites decreases by more than three orders, whereas the thermal conductivity of the same specimen increases very modestly as a function of the filler content.     

Effect of atomic hydrogen adsorption on the transport characteristics of semiconducting carbon nanotubes

The effect of atomic hydrogen adsorption on the conduction and diffusion properties of carbon nanotubes of zigzag type in an external electric field is considered. The model of adsorption of atomic hydrogen on the surface of single-walled carbon nanotubes of zigzag type is based on the single-impurity periodic Anderson model. The theoretical calculation of the diffusion coefficient and electrical conductivity of carbon nanotubes of zigzag type doped with hydrogen atoms is carried out in the relaxation time approximation. It has been revealed that the electrical conductivity and electron diffusion coefficient decrease with increasing concentration of adsorbed hydrogen atoms. It has been shown that the dependence of the electrical conductivity and the diffusion coefficient on the amplitude of the constant electric field at the constant concentration of hydrogen adatoms is nonlinear.     

The electrical conduction variation in stained carbon nanotubes

Carbon nanotubes become stained from coupling with foreign molecules, especially from adsorbing gas molecules. The charge exchange, which is due to the orbital hybridization, occurred in the stained carbon nanotube induces electrical dipoles that consequently vary the electrical conduction of the nanotube. We propose a microscopic model to evaluate the electrical current variation produced by the induced electrical dipoles in a stained zigzag carbon nanotube. It is found that stronger orbital hybridization strengths and larger orbital energy differences between the carbon nanotube and the gas molecules help increasing the induced electrical dipole moment. Compared with the stain-free carbon nanotube, the induced electrical dipoles suppress the current in the nanotube. In the carbon nanotubes with induced dipoles the current increases as a result of increasing orbital energy dispersion via stronger hybridization couplings. In particular, at a fixed hybridization coupling, the current increases with the bond length for the donor-carbon nanotube but reversely for the acceptor-carbon nanotube.     

Effect of uniaxial tensile strength on the electrical properties of doped carbon nanotubes: Density functional theory

We investigated the effect of uniaxial tensile strength on a pristine carbon nanotube, boron-doped carbon nanotube, nitrogen-doped carbon nanotube and co-doped carbon nanotube with boron and nitrogen atoms. To achieve our goal, we performed our calculations with the aid of density functional theory. We studied the changes in the electrical properties after the atomic substitution of a carbon atom by boron, nitrogen, and boron and nitrogen in pristine carbon nanotubes. We also applied uniaxial tensile strength to doped structures as well as pristine one. In addition to studying the band gap, we studied the changes in the Fermi energy, valence bands, and conduction bands. We found that defects as well as stress and strain play a crucial rule on modifying the electrical properties of carbon nanotubes.     

Carbon nanotube-polymer nanocomposites: The role of interfaces

Research aimed at producing new nanocomposites with improved properties has dramatically increased in the last decade, especially on materials tailored at a nanometric level, such as fullerenes and carbon nanotubes. The use of nanoforms as reinforcement of organic polymers has opened the possibility of developing novel ultra-strong and conductive nanocomposites. Nevertheless, the challenge of manufacturing multifunctional composite materials based on nanostructures is still open, in particular in the details of the corresponding interfacial properties, which are particularly relevant in these systems. This paper reviews the main technical activities in this field, focusing on the most important parameters that influence the behavior of their interface, discussing recent advances, as well as current and future trends in research.     

Covalent attachment of polystyrene on multi-walled carbon nanotubes via nitroxide mediated polymerization

A new method to attach polymers on carbon nanotubes has been studied. We used nitroxide mediated polymerization (NMP) to graft polystyrene from multi-walled carbon nanotubes (MWNTs). Carboxyl groups on MWNTs were activated with thionyl chloride (SOCl₂) to give acyl chloride derivative (MWNT-COCl). NMP initiator was introduced to MWNT by esterification of 1-hydroxy-2-phenyl-2-(2′,2′, 6′, 6′-tetramethyl-1′-piperidinyloxy)ethane (HO-PE-TEMPO) with acyl chloride groups of MWNTs. The obtained MWNT-PE-TEMPO was used for initiation of bulk polymerization of styrene, yielding polystyrene-grafted MWNTs (MWNT-g-pSt). The resulting composites of MWNT-g-pSt were analyzed by TEM, SEM, FT-IR and TGA.     

A flexible paper transistor made with aligned single-walled carbon nanotube bonded cellulose composite

We report a flexible paper transistor made with single-walled carbon nanotubes covalently bonded cellulose (SCBC) composite without any additional semiconducting layer. Single-walled carbon nanotubes are covalently grafted to cellulose fibrils in a regenerated cellulose film to form the SCBC composite followed by a mechanical stretching process. The SCBC transistor shows a remarkable current–voltage characteristic depending on the stretching ratio. We found that the alignment of covalently bonded carbon nanotube plays a role that governs the electrical channel behavior of the SCBC composite.